CN111039658A - Phosphorus removal ceramsite and preparation method thereof - Google Patents
Phosphorus removal ceramsite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phosphorus removal ceramsite and a preparation method thereof. The preparation method of the phosphorus removal ceramsite comprises the following steps: 1) the method comprises the following steps of (1) mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to a mass ratio of (7-17): (1-2): (1-2): 1, uniformly mixing, adding water, uniformly stirring, forming and drying to obtain raw material balls; 2) and (3) putting the raw material balls into a sintering furnace, heating to 320-380 ℃ at the speed of 5-10 ℃/min, then preserving heat for pre-sintering, heating to 1000-1100 ℃ at the speed of 5-8 ℃/min, and then preserving heat for sintering. The phosphorus removal ceramsite disclosed by the invention has the advantages of excellent phosphorus removal effect, high mechanical strength, good regeneration performance, high repeated utilization rate and low manufacturing cost, and is convenient for large-scale popularization and application.
Description
Technical Field
The invention relates to a phosphorus removal ceramsite and a preparation method thereof.
Background
The artificial wetland is constructed and operated artificially, is similar to the wetland ground, and mainly utilizes the physical, chemical and biological synergistic effects of soil, artificial media, plants and microorganisms to treat sewage. The action mechanism of the artificial wetland comprises adsorption, detention, filtration, oxidation reduction, precipitation, microbial decomposition, transformation, plant shielding, residue accumulation, transpiration moisture and nutrient absorption and the action of various animals. The artificial wetland has the following advantages: 1) the gravity-flow mode is basically adopted, the energy consumption is basically avoided in the treatment process, the operation cost is low, and the operation cost is about 1/5 of the traditional sewage treatment plant; 2) has stronger removal capability to carbon, nitrogen and phosphorus, and the concentration of the pollutants in the treated effluent can be controlled in a low value range.
In the artificial wetland system, due to the synergistic effect of plants, soil (filling materials) and microorganisms, the artificial wetland system has strong treatment capacity on pollutants containing carbon, nitrogen and phosphorus. Carbon and nitrogen elements in the artificial wetland system can be absorbed by plants to synthesize self substances and transferred from the water body, and can also be transferred from the water body in a gas form through the respiration and decomposition of microorganisms, so that the artificial wetland system can be ensured to maintain a good treatment effect on pollutants such as COD (chemical oxygen demand), ammonia nitrogen and the like. The phosphorus in the artificial wetland system is converted through the modes of soil (filler) adsorption, plant absorption and microbial substance synthesis, and the phosphorus is released again after the microorganisms die, so that the phosphorus can be actually only harvested through vegetation and replaced and transferred through the soil (filler). However, the adsorption capacity of soil or traditional fillers to phosphorus is very limited, and the artificial wetland system is easily saturated by adsorption, so that the removal effect of total phosphorus is greatly weakened, and the final effluent quality is difficult to meet the requirements.
In order to improve the effect of the constructed wetland on removing total phosphorus in the water body, the method for adding the filler with strong phosphorus adsorption capacity is a common method at present. The existing artificial wetland phosphorus removal filler is mainly materials such as zeolite, ferrovanadium, kaolin and the like containing metal ions, and although the materials have stronger adsorption capacity to soluble phosphate in water, the materials still have the following defects: 1) the material has less pore structure and high compactness, and the adsorption to phosphorus is usually only carried out on the surface, so that the processing capacity is relatively low; 2) the material has an excessively small particle size, so that pores and pipelines of the artificial wetland are easily blocked, and the problems of reduced flow capacity, uneven flow and the like of the wetland are caused; 3) the material is associated with more heavy metals, and the dissolution of the heavy metals causes new risks to the water environment; 4) the material is difficult to regenerate and difficult to recycle after saturated adsorption.
Therefore, it is necessary to develop a phosphorus removal filler for artificial wetlands, which has excellent phosphorus removal effect, good regeneration performance and high recycling rate.
Disclosure of Invention
The invention aims to provide a phosphorus removal ceramsite and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the phosphorus-removing ceramsite comprises the following steps:
1) the method comprises the following steps of (1) mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to a mass ratio of (7-17): (1-2): (1-2): 1, uniformly mixing, adding water, uniformly stirring, forming and drying to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 320-380 ℃ at the speed of 5-10 ℃/min, then preserving heat for pre-sintering, heating to 1000-1100 ℃ at the speed of 5-8 ℃/min, preserving heat for sintering, and obtaining the phosphorus removal ceramsite.
Preferably, the particle size of the dry bottom mud and the fly ash in the step 1) is less than 150 μm.
Preferably, the dry bottom mud in the step 1) comprises the following components in percentage by mass: SiO 22：48％～70％；Al2O3：10％～25％；Fe2O3: 3% -12%; K. oxides of Na, Ca and Mg: 1.5 to 12 percent.
Preferably, the fly ash in the step 1) comprises the following components in percentage by mass: SiO 22：40％～45％；Al2O3：15％～20％；Fe2O3: 2% -5%; K. oxides of Na, Ca and Mg: 3 to 8 percent.
Preferably, the diameter of the raw meal ball in the step 1) is less than 10 mm.
Preferably, the pre-sintering time in the step 2) is 20-40 min.
Preferably, the sintering time in the step 2) is 10-20 min.
The invention has the beneficial effects that: the phosphorus removal ceramsite disclosed by the invention has the advantages of excellent phosphorus removal effect, high mechanical strength, good regeneration performance, high repeated utilization rate and low manufacturing cost, and is convenient for large-scale popularization and application.
1) The iron powder is used as the adsorbent of the soluble phosphate in the water body, so that the risk of heavy metal release is avoided, and the effluent safety of the constructed wetland is guaranteed;
2) according to the invention, iron powder is added in the ceramsite manufacturing process, so that active sites and water flow channels can be provided for iron ions by fully utilizing pores of the ceramsite, the phosphorus adsorption performance of the ceramsite and the iron ions is greatly improved, and the effluent standard reaching rate and phosphorus removal efficiency of the artificial wetland are improved;
3) according to the invention, the ceramsite with a porous structure and high mechanical strength is used as the carrier of the iron, so that the mechanical strength of the powdered iron is improved, the problems that the traditional mineral filler is low in mechanical strength and easy to block wetland pores and further reduce the wetland overflowing capacity are solved, and the effective operation of the constructed wetland is ensured;
4) the phosphorus removal ceramsite is porous particles, is easy to collect for the second time, can be reduced by using strong acid, and greatly improves the regeneration performance and the repeated utilization rate;
5) the invention utilizes the bottom mud, the fly ash and the plant straws to manufacture the ceramsite, thereby reducing the cost and achieving the purpose of recycling the wastes on the one hand.
Drawings
Fig. 1 is an SEM image of a cross-section of the phosphorus removing ceramsite of example 1.
FIG. 2 is an SEM image of the cross section of a commercial ceramsite of a comparative example.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
The indexes of the raw materials in examples 1 to 4 are as follows:
bottom mud: desilting bottom mud, SiO for treating certain middle and small rivers in the north of Guangdong province265.13% of Al2O314.28% of Fe2O3The content of the organic matter is 3.72 percent, the content of the oxides of K, Na, Ca and Mg is 10.76 percent, and the content of the organic matter is 4.03 percent;
fly ash: industrial tailings of a coal-fired power plant, SiO, in Guangzhou City241.25% of Al2O317.37% of Fe2O3The content is 3.16 percent, and the content of the oxides of K, Na, Ca and Mg is 5.39 percent;
plant straw: canna harvested in the artificial wetland of the Guangdong province profit test base;
iron powder: goethite powder, with an iron content of 62.3%, was dark brown in color and had a specific gravity of 3.9.
Example 1:
a dephosphorizing ceramsite and a preparation method thereof comprise the following steps:
1) naturally drying and dehydrating the bottom mud, then placing the bottom mud in an oven to dry at 105 ℃, grinding and crushing the bottom mud, and then sieving the ground bottom mud by a 100-mesh sieve to obtain dry bottom mud; crushing the fly ash and sieving the crushed fly ash with a 100-mesh sieve; cutting plant straws into small sections with the length of 10cm, then placing the small sections in an oven to be dried at 105 ℃, and crushing the small sections to obtain dry plant straw powder; uniformly mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to a mass ratio of 17:1:1:1, adding water, uniformly stirring, making into balls by a ball making machine with an inner diameter of 10mm, and drying in an oven at 105 ℃ to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 350 ℃ at the speed of 10 ℃/min, then preserving heat and presintering for 30min, heating to 1100 ℃ at the speed of 5 ℃/min, and then preserving heat and sintering for 15min to obtain the phosphorus removal ceramsite (with the average particle size of 10 mm).
Example 2:
a dephosphorizing ceramsite and a preparation method thereof comprise the following steps:
1) naturally drying and dehydrating the bottom mud, then placing the bottom mud in an oven to dry at 105 ℃, grinding and crushing the bottom mud, and then sieving the ground bottom mud by a 100-mesh sieve to obtain dry bottom mud; crushing the fly ash and sieving the crushed fly ash with a 100-mesh sieve; cutting plant straws into small sections with the length of 10cm, then placing the small sections in an oven to be dried at 105 ℃, and crushing the small sections to obtain dry plant straw powder; uniformly mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to a mass ratio of 15:2:2:1, adding water, uniformly stirring, making into balls by a ball making machine with an inner diameter of 10mm, and drying in an oven at 105 ℃ to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 350 ℃ at the speed of 10 ℃/min, then preserving heat and presintering for 30min, heating to 1100 ℃ at the speed of 5 ℃/min, and then preserving heat and sintering for 15min to obtain the phosphorus removal ceramsite.
Example 3:
a dephosphorizing ceramsite and a preparation method thereof comprise the following steps:
1) naturally drying and dehydrating the bottom mud, then placing the bottom mud in an oven to dry at 105 ℃, grinding and crushing the bottom mud, and then sieving the ground bottom mud by a 100-mesh sieve to obtain dry bottom mud; crushing the fly ash and sieving the crushed fly ash with a 100-mesh sieve; cutting plant straws into small sections with the length of 10cm, then placing the small sections in an oven to be dried at 105 ℃, and crushing the small sections to obtain dry plant straw powder; uniformly mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to the mass ratio of 7:1:1:1, adding water, uniformly stirring, making into balls by a ball making machine with the inner diameter of 10mm, and drying in an oven at 105 ℃ to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 350 ℃ at the speed of 10 ℃/min, then preserving heat and presintering for 30min, heating to 1000 ℃ at the speed of 5 ℃/min, and then preserving heat and sintering for 15min to obtain the phosphorus removal ceramsite.
Example 4:
a dephosphorizing ceramsite and a preparation method thereof comprise the following steps:
1) naturally drying and dehydrating the bottom mud, then placing the bottom mud in an oven to dry at 105 ℃, grinding and crushing the bottom mud, and then sieving the ground bottom mud by a 100-mesh sieve to obtain dry bottom mud; crushing the fly ash and sieving the crushed fly ash with a 100-mesh sieve; cutting plant straws into small sections with the length of 10cm, then placing the small sections in an oven to be dried at 105 ℃, and crushing the small sections to obtain dry plant straw powder; uniformly mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to the mass ratio of 7:1:1:1, adding water, uniformly stirring, making into balls by a ball making machine with the inner diameter of 10mm, and drying in an oven at 105 ℃ to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 350 ℃ at the speed of 10 ℃/min, then preserving heat and presintering for 30min, heating to 1000 ℃ at the speed of 5 ℃/min, and then preserving heat and sintering for 20min to obtain the phosphorus removal ceramsite.
Comparative example:
the commercial ceramsite comprises: the average particle size is 10mm, the manufacturing raw materials are clay, fly ash and foaming agent, and no iron powder is added.
And (3) performance testing:
1) the cross sections of the dephosphorizing ceramsite of example 1 and the commercially available ceramsite of the comparative example were observed by using a scanning electron microscope, and the obtained SEM images are shown in fig. 1 and 2.
As can be seen from fig. 1 and 2: compared with the commercially available ceramsite, the phosphorus removal ceramsite in the embodiment 1 has a richer pore structure, and the macropores, the mesopores and the micropores are distributed relatively and uniformly, so that the rich pore structure not only can provide a favorable channel for pollutant diffusion and adsorption, but also can provide a space for microorganism attachment and wetland plant root growth. Therefore, the phosphorus removal ceramsite has excellent structural performance.
2) Phosphorus removal performance experiment: selecting 5 conical flasks, adding 200mL of water samples with the total phosphorus concentration of 8mg/L respectively, adding 3g of the phosphorus removal ceramsite of the examples 1-4 and the commercially available ceramsite of the comparative example respectively, placing the conical flasks in a constant temperature oscillator (at the temperature of 25 ℃ and the rotating speed of 120rpm), oscillating for 36 hours, and then detecting the total phosphorus concentration in the water samples, wherein the test results are shown in the following table:
TABLE 1 phosphorus removal Performance test results
As can be seen from Table 1: the phosphorus removal ceramsite disclosed by the invention has extremely high adsorption capacity on total phosphorus, the average value of the concentration of the total phosphorus in effluent is 0.19mg/L, the corresponding removal rate is about 98%, the adsorption capacity reaches 520mg/kg, while the removal rate of the commercially available ceramsite on the total phosphorus is only 61%, and the adsorption capacity is only 323 mg/kg.
3) Regeneration performance test: respectively adding 2g of the phosphorus removal ceramsite of the examples 1-4 with saturated adsorption and the commercial ceramsite of the comparative example into 5 conical flasks, then respectively adding 100mL of hydrochloric acid with the concentration of 0.4mol/L, then placing the conical flasks in a constant temperature oscillator (the temperature is 25 ℃, the rotating speed is 120rpm) to oscillate for 24 hours, then measuring the total phosphorus concentration in the hydrochloric acid, and calculating the desorption rate of the total phosphorus, wherein the results are shown in the following table:
table 2 desorption rate test results for total phosphorus
| Test index | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Desorption ratio of total phosphorus (%) | 98 | 98 | 96 | 95 | 98 |
As can be seen from Table 2: the dephosphorizing ceramsite and the commercially available ceramsite have the capability of complete regeneration.
4) The artificial wetland application experiment comprises the following steps:
2 vertical subsurface flow constructed wetlands (single pool area 55 m) are built in Guangdong provincial profit test base2Length-width ratio of 11:5), the size, water distribution mode and original effluent of 2 tanks are all the same, phosphorus removal ceramsite of example 1 with thickness of 10cm is paved in a No. 1 tank below 30cm of surface matrix soil (lower filler is coarse sand and gravel), market ceramsite with thickness of 10cm is paved in a No. 2 tank below 30cm of surface matrix soil (lower filler is the same as the No. 1 tank), and the daily treatment scale of the wetland is 13m3The average value of the total phosphorus concentration of inlet water is 6.84mg/L, the average concentration of the total phosphorus after pretreatment in the integrated purification tank is 4.96mg/L (namely the total phosphorus concentration of inlet water of the artificial wetland), and the total phosphorus concentration of outlet water after purification in 2 artificial wetlands (the operation time is 1 year) is shown in the following table:
TABLE 3 Total phosphorus removal effect of constructed wetlands with different fillers
As can be seen from Table 3: the dephosphorizing ceramsite disclosed by the invention is used as the artificial wet filler, the average concentration of the total phosphorus in the effluent is 0.14mg/L, and the total phosphorus removal rate of the wetland is up to 97%, while the commercially available ceramsite is used as the artificial wet filler, the average concentration of the total phosphorus in the effluent is 1.04mg/L, and the total phosphorus removal rate of the wetland is only 78%. Therefore, the phosphorus removal ceramsite can greatly improve the phosphorus removal effect of the artificial wetland and ensure that the quality of the effluent water is stable and reaches the standard.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of phosphorus-removing ceramsite is characterized by comprising the following steps: the method comprises the following steps:
1) the method comprises the following steps of (1) mixing dry bottom mud, fly ash, dry plant straw powder and iron powder according to a mass ratio of (7-17): (1-2): (1-2): 1, uniformly mixing, adding water, uniformly stirring, forming and drying to obtain raw material balls;
2) and (3) putting the raw material balls into a sintering furnace, heating to 320-380 ℃ at the speed of 5-10 ℃/min, then preserving heat for pre-sintering, heating to 1000-1100 ℃ at the speed of 5-8 ℃/min, preserving heat for sintering, and obtaining the phosphorus removal ceramsite.
2. The method of claim 1, wherein: the particle size of the dry bottom mud and the fly ash in the step 1) is less than 150 mu m.
3. The production method according to claim 1 or 2, characterized in that: the dry bottom mud in the step 1) comprises the following components in percentage by mass: SiO 22：48％～70％；Al2O3：10％～25％；Fe2O3: 3% -12%; K. oxides of Na, Ca and Mg: 1.5 to 12 percent.
4. The production method according to claim 1 or 2, characterized in that: the fly ash in the step 1) comprises the following components in percentage by mass: SiO 22：40％～45％；Al2O3：15％～20％；Fe2O3: 2% -5%; K. oxides of Na, Ca and Mg: 3 to 8 percent.
5. The production method according to claim 1 or 2, characterized in that: the diameter of the raw material ball in the step 1) is less than 10 mm.
6. The method of claim 1, wherein: and step 2), the pre-sintering time is 20-40 min.
7. The production method according to claim 1, 2 or 6, characterized in that: and 2) sintering for 10-20 min.
8. A phosphorus removal ceramsite which is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The application of the dephosphorizing ceramsite of claim 8 as the dephosphorizing filler for artificial wetland.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848130A (en) * | 2020-08-19 | 2020-10-30 | 南通大学 | Modified ceramsite capable of efficiently removing phosphorus and preparation method thereof |
| CN112341244A (en) * | 2020-11-18 | 2021-02-09 | 合肥工业大学 | Method for preparing phosphorus removing agent by using mine waste residues |
| CN113244880A (en) * | 2021-06-16 | 2021-08-13 | 南通大学 | Sintered ceramsite capable of efficiently removing phosphorus, preparation method and regeneration method thereof |
| CN114409029A (en) * | 2022-02-12 | 2022-04-29 | 尚川（北京）水务有限公司 | Phosphorus removal ceramsite, preparation method and application thereof |
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